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<p>Transition metals (TMs) typically exhibit rich redox chemistry and can be found in various oxidation states. In most cases, TMs are positively charged. Strong <i>π</i>-accepting ligands have been shown to stabilize molecular complexes with TMs in formal negative oxidation states. By contrast, organic-ligand-free TM anions remain rare, limited to intermetallic compounds based on third-row TMs such as gold or platinum. Here we report the synthesis of air-stable lanthanide–nickel molecular intermetallic complexes featuring a ligand-free Ni<sup>2−</sup> confined within fullerenes, namely, Tb<sub>2</sub>Ni@C<sub>82</sub>. The charged Tb<sub>2</sub>Ni lanthanide nickelide cluster forms metal-only Lewis pairs, featuring strongly polarized Tb–Ni covalent bonds with short bond lengths in the range of 2.50–2.57 Å. X-ray absorption spectroscopy supports the −2 oxidation state of Ni with 3<i>d</i><sup>10</sup>4<i>s</i><sup>2</sup> electron count, in line with the spectroscopic and magnetic measurements, and theoretical study. This finding opens up an efficient way to stabilize intermetallic clusters with elusive nucleophilic TM anions by confining them inside molecular carbon cages.</p><p></p>

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Lanthanide–nickel molecular intermetallic complexes featuring a ligand-free Ni2− anion in endohedral fullerenes

  • 期刊论文

  • 发表日期：

    2025年4月23日

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  • Panfeng Chuai,
  • Ziqi Hu,
  • Yang-Rong Yao,
  • Zhanxin Jiang,
  • Aman Ullah,
  • Ya Zhao,
  • Weiren Cheng,
  • Muqing Chen,
  • Eugenio Coronado,
  • Shangfeng Yang,
  • Zujin Shi

摘要

Transition metals (TMs) typically exhibit rich redox chemistry and can be found in various oxidation states. In most cases, TMs are positively charged. Strong π-accepting ligands have been shown to stabilize molecular complexes with TMs in formal negative oxidation states. By contrast, organic-ligand-free TM anions remain rare, limited to intermetallic compounds based on third-row TMs such as gold or platinum. Here we report the synthesis of air-stable lanthanide–nickel molecular intermetallic complexes featuring a ligand-free Ni2− confined within fullerenes, namely, Tb2Ni@C82. The charged Tb2Ni lanthanide nickelide cluster forms metal-only Lewis pairs, featuring strongly polarized Tb–Ni covalent bonds with short bond lengths in the range of 2.50–2.57 Å. X-ray absorption spectroscopy supports the −2 oxidation state of Ni with 3d104s2 electron count, in line with the spectroscopic and magnetic measurements, and theoretical study. This finding opens up an efficient way to stabilize intermetallic clusters with elusive nucleophilic TM anions by confining them inside molecular carbon cages.